US3046244A - Method of preparing a solution of butyl rubber in hexane comprising adding wet butyl rubber to an agitated mixture of hexane and water - Google Patents

Method of preparing a solution of butyl rubber in hexane comprising adding wet butyl rubber to an agitated mixture of hexane and water Download PDF

Info

Publication number
US3046244A
US3046244A US578965A US57896556A US3046244A US 3046244 A US3046244 A US 3046244A US 578965 A US578965 A US 578965A US 57896556 A US57896556 A US 57896556A US 3046244 A US3046244 A US 3046244A
Authority
US
United States
Prior art keywords
water
hexane
polymer
butyl rubber
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US578965A
Other languages
English (en)
Inventor
Hunter Edward Allen
Lambert Merlan Meredith
Segura Marnell Albin
Small Augustus Bailey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL216461D priority Critical patent/NL216461A/xx
Priority to NL97979D priority patent/NL97979C/xx
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US578965A priority patent/US3046244A/en
Priority to GB11778/57A priority patent/GB847525A/en
Priority to FR1186962D priority patent/FR1186962A/fr
Application granted granted Critical
Publication of US3046244A publication Critical patent/US3046244A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media

Definitions

  • This invention relates to a method for preparing solutions of natural and synthetic polymers and resins and to the preparation of latices therefrom.
  • polymers may be dissolved in suitable solvents simply by adding the polymer to the solvent, preferably in the form of discrete particles, while stirring and even heating to facilitate solution.
  • the resulting solution is exceedingly viscous and tacky. This renders the polymer solution difficult to handle and slows the rate at which the polymer goes into solution.
  • the viscosity problem assumes large proportions and is therefore economically disadvantageous.
  • This problem is particularly critical with respect to those polymers which occur or are prepared as dispersions in water, such as natural rubber and the synthetic polymers, butyl rubber copolymer of isobutylene and small amounts of diolefins as defined in Hackhs Chemical Dictionary, third edition, the copolymers of isobutylene and styrene, and polyisobutylene.
  • the dispersions of the synthetic polymers are formed by dumping the reactor efiluent into hot water containing a dispersing agent, such as zinc steal-ate, to volatilize the diluents and unreacted monomers and form a coarse dispersion. This dispersion is not stable since it is too coarse.
  • the polymer must be removed from the water and dried in the form of crumb before being dissolved in a hydrocarbon solvent, if the ditficulties of excessive viscosity are to be avoided.
  • any method of drying which removes all the water from the polymer causes the polymer to break down in molecular weight, making it impossible to prepare solutions or latices from polymer of maximum molecular weight produced in the plant.
  • Another object of this invention is to provide a method for preparing latices from the very highest molecular weight polymers.
  • a further important object of this invention is to prepare latices directly from polymer in the form of wet crumb without the attendant viscosity difiicul-ties.
  • Another important object of the invention is to provide a method for simultaneously dissolving a solid polymer in a suitable solvent and dispersing it in Water.
  • the polymer goes into solution smoothly without excessivee increase in viscosity, forming a solution of polymer in the solvent which in turn is dispersed in water as the continuous phase.
  • the polymer maybe employed in the form of wet crumb (containing up to 50% water) in which case it may be desirable to add additional solvent to compensate for the water added by the wet crumb.
  • emulsifying agents are used in preparing the solventwater emulsion, they may be any type of agent adapted for preparing an oil-in-water emulsion. They may be desirably selected in accordance with the end use of the polymer solution. If the emulsion is to be broken to recover the non-aqueous phase, then emulsifiers forming quick-breaking emulsions, such as soap solutions, may be used. However, if a stable polymer-Water latex is desired then the emulsifiers should be those suitable for forming stable polymer latices, such as, for example, the anionic,
  • emulsifiers and emulsifier combinations disclosed in copending application of Charlet and Small, Serial No. 521, 872, filed July 15, 1955 and incorporated herein by reference.
  • the amount of emulsifier to be used may vary but a desirable amount is enough to leave less than 5.0 wt. percent, based on polymer, in the final solution or latex.
  • the polymer-solvent-water system is to be converted to a polymenwater latex it is desirably passed through a suitable homogenizer such as a colloid mill, 2. dispersator, a Waring Blendor, a sonic mixer or the like with or without the use of additional emulsifying agents.
  • a suitable homogenizer such as a colloid mill, 2. dispersator, a Waring Blendor, a sonic mixer or the like with or without the use of additional emulsifying agents.
  • the homogenized emulsion is then stripped to remove the hycarbon solvent, leaving the finished latex which is passed to storage.
  • the polymers which may be emulsified in accordance with the present invention include natural rubber, polyisobutylene, various synthetic rubbers such as butyl rubber (a copolymer of 97% isobutylene and 3% isoprene), GRS (a copolymer of butadiene and styrene prepared by emulsion polymerization), polybutadiene and copolymers of butadiene and styrene prepared by mass polymerization with sodium, GR-N or Paracril (a copolymer of butadiene and acrylonitrile prepared by emulsion polymerization), and resins such as the copolymers of isobutylene and styrene (prepared at low temperatures with Friedel-Crafts catalysts) and petroleum resins (prepared from steam-cracked petroleum streams, such as naphtha, kerosene or gas oil by the use of Friedel-Crafts catalysts at low temperatures) as well as any other waterinsoluble solid poly
  • Suitable solvents which may be emulsified with water and used to dissolve the polymer may be any liquid in which the polymer is soluble, such as for example the hydrocarbon solvents hexane, heptane, octane, isooctane, the nonanes, the decanes, naphtha fractions, benzene, toluene, Varsol, Solvesso 100 (a substantially 100% aromatic hydrocarbon fraction boiling 315350 F.) and Solvesso 150 (a substantially 100% aromatic hydrocarbon fraction boiling 365-415 F.), cyclohexane, and cyclohexene, carbon tetrachloride, trichloroethylene, carbon disulfide, and the like. More volatile solvents can be used but pressure equipment would be required to minimize evaporation losses.
  • the water used is preferably distilled or natural soft water but most waters suitable for human consumption can be used.
  • Hard Waters may require preliminary chemical treatment to precipitate the polyvalent minerals thereof in the form of stable compounds which will remain inert to the emulsion ingredients if the precipitated compounds are left in the completed emulsion.
  • the amount of water contained in the initial emulsion of hydrocarbon solvent and water is not critical as long as there is enough water present to produce a final stable latex, if such is desired.
  • the original hydrocarbonsolvent-water emulsion may be composed of from 1 part to 3 parts by weight of hydrocarbon solvent per part of water.
  • the final ratio of hydrocarbon solvent to water to polymer may vary over a wide range. However, a suitable ratio has been found to be about 3 parts by weight of hydrocarbon to 2 parts of water to 1 part of polymer. After stripping to remove the hydrocarbon, it is desirable to have as concentrated a latex as possible, particularly for shipping purposes.
  • hexane, water and any emulsifiers are introduced through lines 1, Z and 3, respectively, into the emulsion preparation vessel 4, provided with stirrer 5.
  • the resulting emulsion of hexane in water is withdrawn from vessel 4 through lined? and introduced into rubber solution vessel 7 provided with stirrer 8.
  • Solid particles of rubber, such as wet crumb is introduced into the pool of hexane-water emulsion in vessel 7 through line 9.
  • stirrer 8 Upon agitation with stirrer 8, the rubber goes quickly into solution in the hexane and the resulting hexane-rubber solution immediately forms as the discontinuous phase of the emulsion.
  • the emulsion is withdrawn from vessel 7 through line 10 and introduced into homogenizer 11.
  • This may be a dispersator, a sonic mixer, a colloid mill, a Waring Blendor or the like, or a combination of any of these and may be in one or a plurality of units.
  • the now finely divided dispersion is passed by line 12 into stripper 13 where the hydrocarbon solvent is removed in any suitable manner as by contact with steam or other hot gases.
  • the water content may be simultaneously reduced to give a final concentrated latex. Hexane and any water are removed overhead through line 14 and condensed in vessel 15 where it is stored and recycled as desired to line 1 through line 16. Finished latex is removed through line 17 and passed to storage.
  • Example 11 250 grams of dry crumb butyl rubber having a Staudinger mol. wt. of 300,000-330,000 was added to the following agitated mixture:
  • Example 111 250 grams of a copolymer of 50% isobutylene and 50% styrene was added to the recipe of Example I in the form of dense inch cubes and agitated for six hours. An emulsion containing 3 wt. percent of solids was obtained representing 27% of polymer dissolved in the hexane.
  • Example IV Equal quantities (1500 cc. each) of water and hexane were agitated without an emulsifier and while the agitation was continued 250 grams of dry crumb butyl rubber (Staudinger mol. wt. 400,000-420,000) Were blended in r and the agitation continued for six hours. After the agitation was stopped, the phases quickly separated. The butyl rubber was found to have dissolved in hexane, forming a solution containing 21.7 wt. percent solids.
  • Example V sion 13.3 wt. percent solids, and the high molecular weight butyl rubber 13.8 wt. percent solids.
  • Example V1 TO a high-shear type of agitator known as the Dispersator and manufactured by Premier Mills Co., there was added the following materials in the order listed:
  • Example 11 shows that the predispersion of the solvent in water reduces the viscosity considerably, from 1275 centipoises to 194 centipoises, in the particular instance.
  • Example IV shows, it is not necessary to use an emulsifier with the mixture of solvent and water, it is only necessary to use constant agitation.
  • Example VI shows, the emulsion is very stable and can be stored for a reasonable period of time with little change in physical properties. It can also be stripped to form a stable latex.
  • a method which comprises providing a wet solid rubbery copolymer of butyl rubber containing between about 27 and 50% by weight of Water therein; forming a violently agitated mixture of 1 to 3 parts of hexane dispersed in 1 part of water as the continuous phase; and adding said wet rubbery copolymer directly to said agitated mixture to provide a solution of rubbery polymer in said hexane, with a relatively low viscosity.
  • a method which comprises providing a wet solid rubbery copolymer of 97% isobutylene with 3% isoprene containing between about 27 and 50% by weight of water therein; forming a violently agitated emulsion of 1 to 3 parts of hexane dispersed in 1 part of water as the continuous phase; adding said wet rubbery copolymer directly to said agitated emulsion to provide a solution of rubbery polymer dissolved in said hexane with a relatively low viscosity, said solution being dispersed in water; and stripping the solvent from the dispersion to provide an aqueous latex with fine polymer particles therein.
  • a method which comprises providing a wet solid rubbery copolymer of 97% isobutylene with 3% isoprene containing about 27% by weight of water therein; forming a violently agitated mixture of 1 to 3 parts of hexane dispersed in 1 part of water as the continuous phase; and adding said wet rubbery copolymer directly to said agitated mixture to provide a solution of rubbery polymer in said hexane, with a relatively low viscosity.
  • a method which comprises providing a Wet solid rubbery copolymer of 97% isobutylene with 3% isoprene containing 50% by weight of water therein; forming a violently agitated mixture of 1 to 3 parts of hexane dispersed in 1 part of water as the continuous phase; and adding said wet rubbery copolymer directly to said agitated mixture to provide a solution of rubbery polymer in said hexane, with a relatively low viscosity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US578965A 1956-04-18 1956-04-18 Method of preparing a solution of butyl rubber in hexane comprising adding wet butyl rubber to an agitated mixture of hexane and water Expired - Lifetime US3046244A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL216461D NL216461A (en(2012)) 1956-04-18
NL97979D NL97979C (en(2012)) 1956-04-18
US578965A US3046244A (en) 1956-04-18 1956-04-18 Method of preparing a solution of butyl rubber in hexane comprising adding wet butyl rubber to an agitated mixture of hexane and water
GB11778/57A GB847525A (en) 1956-04-18 1957-04-10 Preparing polymer solutions and emulsions
FR1186962D FR1186962A (fr) 1956-04-18 1957-04-12 Procédé de préparation de solutions et d'émulsions de polymères

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US578965A US3046244A (en) 1956-04-18 1956-04-18 Method of preparing a solution of butyl rubber in hexane comprising adding wet butyl rubber to an agitated mixture of hexane and water

Publications (1)

Publication Number Publication Date
US3046244A true US3046244A (en) 1962-07-24

Family

ID=24315053

Family Applications (1)

Application Number Title Priority Date Filing Date
US578965A Expired - Lifetime US3046244A (en) 1956-04-18 1956-04-18 Method of preparing a solution of butyl rubber in hexane comprising adding wet butyl rubber to an agitated mixture of hexane and water

Country Status (4)

Country Link
US (1) US3046244A (en(2012))
FR (1) FR1186962A (en(2012))
GB (1) GB847525A (en(2012))
NL (2) NL97979C (en(2012))

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285869A (en) * 1962-03-05 1966-11-15 Shell Oil Co Emulsions and latices of cis 1, 4-polyisoprene
US4455265A (en) * 1982-03-03 1984-06-19 The Firestone Tire & Rubber Company Stabilizer for low ammonia natural rubber latex compounds

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3310515A (en) * 1963-01-11 1967-03-21 Shell Oil Co Preparation of latices from organic solvent solutions of elastomers
CA1105632A (en) * 1977-03-10 1981-07-21 John R. Adams Process for making polymer solutions

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB363681A (en) * 1930-04-14 1931-12-14 Elektrochem Werke Muenchen Ag Process for the production of colloidal dispersions
US1909080A (en) * 1929-04-25 1933-05-16 Strauch Clauss Burkart Lubricating and cooling material
GB515763A (en) * 1938-06-11 1939-12-13 Dewey And Almy Chem Comp Improvements relating to dispersions of rubber
US2296427A (en) * 1938-07-04 1942-09-22 Jasco Inc Process of producing aqueous dispersions of polyisobutylene
US2313144A (en) * 1938-06-07 1943-03-09 Ici Ltd Production of aqueous dispersions of ethylene polymer
US2595797A (en) * 1949-06-11 1952-05-06 Standard Oil Dev Co Process of producing aqueous dispersions of rubberlike plastics
US2799662A (en) * 1953-03-18 1957-07-16 Esso Rescarch And Engineering Process for producing aqueous dispersions of elastomers

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1909080A (en) * 1929-04-25 1933-05-16 Strauch Clauss Burkart Lubricating and cooling material
GB363681A (en) * 1930-04-14 1931-12-14 Elektrochem Werke Muenchen Ag Process for the production of colloidal dispersions
US2313144A (en) * 1938-06-07 1943-03-09 Ici Ltd Production of aqueous dispersions of ethylene polymer
GB515763A (en) * 1938-06-11 1939-12-13 Dewey And Almy Chem Comp Improvements relating to dispersions of rubber
US2296427A (en) * 1938-07-04 1942-09-22 Jasco Inc Process of producing aqueous dispersions of polyisobutylene
US2595797A (en) * 1949-06-11 1952-05-06 Standard Oil Dev Co Process of producing aqueous dispersions of rubberlike plastics
US2799662A (en) * 1953-03-18 1957-07-16 Esso Rescarch And Engineering Process for producing aqueous dispersions of elastomers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285869A (en) * 1962-03-05 1966-11-15 Shell Oil Co Emulsions and latices of cis 1, 4-polyisoprene
US4455265A (en) * 1982-03-03 1984-06-19 The Firestone Tire & Rubber Company Stabilizer for low ammonia natural rubber latex compounds

Also Published As

Publication number Publication date
NL216461A (en(2012))
NL97979C (en(2012))
GB847525A (en) 1960-09-07
FR1186962A (fr) 1959-09-04

Similar Documents

Publication Publication Date Title
US2799662A (en) Process for producing aqueous dispersions of elastomers
US3238173A (en) Polystyrene-polyisoprene-polystyrene block copolymer latices and process for their preparation
EP0010986B2 (en) Process for the preparation of polymer latex
JP5031821B2 (ja) 人工ラッテクスの調製方法
DE69205931T2 (de) Copolymere Dispersion in aliphatischen Lösungsmitteln.
KR20110039315A (ko) 인공 라텍스의 제조방법
US4418185A (en) Process for nonaqueous dispersion polymerization of butadiene in the presence of high cis-1,4-polyisoprene as a polymeric dispersing agent
US3301810A (en) Isoolefin-multiolefin copolymers through ultrasonic homogenizers
US2933468A (en) Emulsifiers from hydrocarbon polymer, maleic anhydride, and polyalkylene oxide glycol, emulsion containing same and methods for making thereof
US3976609A (en) Process for the preparation of distributions
US3046244A (en) Method of preparing a solution of butyl rubber in hexane comprising adding wet butyl rubber to an agitated mixture of hexane and water
US3285869A (en) Emulsions and latices of cis 1, 4-polyisoprene
US3642676A (en) Preparation of artificial latexes of olefin polymers
US3277037A (en) Preparation of latices
EP0106785B1 (en) Process for nonaqueous dispersion polymerization of butadiene in the presence of carbonylated polymeric dispersing agents
US4508881A (en) Process for nonaqueous dispersion polymerization of butadiene in the presence of polymeric dispersing agents
US3243400A (en) Process and apparatus for emulsifying butyl rubber
Dewald et al. PVC miniemulsion polymerization. I. Origin of droplet families
US3499059A (en) Method of making toughened polymers from emulsions of immiscible solutions of elastomers,thermoplastic polymers and ethylenically unsaturated monomers stabilized by the addition of block or graft copolymers
US3310516A (en) Alcohol addition subsequent to emulsification
US2912401A (en) Stripping solvent from isobutylene-isoprene copolymer latices
US2568950A (en) Latices from alkali metal catalyzed polymers
US3839258A (en) Process of preparing a latex of an organic polymer from a solution of this polymer in an organic solvent
US2655496A (en) Method for emulsifying polymerizable compounds and effecting polymerization with the emulsions
US3071555A (en) Process for preparing aqueous dispersion or solvent solution of olefin polymer from polymerization slurry